Matted polyamide-pud

ABSTRACT

Polymers are disclosed that incorporate portions of secondary or tertiary polyamide segments connected with polyisocyanates. These polymers have enhanced matting properties. The enhanced matting properties are from creating an inherently matt surface from the polymer without the use of any separate fine particle size matting additives. Conventional matting agents such as fine particle size silica usually results in loss of physical properties such as haze development and porosity in the coating from the matting agent. Composites and hybrids of these polymers and other polyamides, polyurethane with vinyl polymers (acrylates) are also disclosed and claimed.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority from PCT Application Serial No.PCT/US2018/030232 filed on Apr. 30, 2018, which claims the benefit ofU.S. Provisional Application No. 62/491,802 filed on Apr. 28, 2017.

FIELD OF INVENTION

The invention relates to water borne polymer containing polyamide andmultiple urethane and/or urea linkages dispersions comprising polyamidesegments derived from cyclic aliphatic or aromatic primary or secondaryamines reacted with some form of reactive carbonyl such as carboxylicacids. These polyamides unexpected impart a texture to the surface ofcoatings derived from said polymer containing polyamide and multipleurethane and/or multiple urea linkages dispersions that is characterizedby a lowered gloss reading.

BACKGROUND OF THE INVENTION

In the coatings industry sometimes a high gloss very smooth coatingfinish is desired. At other times a matted (lower gloss) coating or inksurface is desired that reflects incident light in a variety ofdirections due to the coating's surface variations. A variety ofmechanisms and products for imparting gloss reduction (matting) havebeen developed for different types of coatings (solvent based and waterbased). The coatings industry desires uniformity and consistent controlof the extent of matting and the ability to adjust the level of mattingeasily at any stage of the coating manufacture and coating applicationprocesses.

Silica with controlled particle size has been used extensively inproducing matte finishes. It is believed to function by the silicaparticles extending out of the coating surface creating high spots onthe coating surface that reflect light in a variety of directions. Thesilica used in this application has a porous structure that increasesthe porosity of the finished coating (more silica, more matting, andmore porosity). Porosity in a coating decreases its resistance tovarious liquids that might discolor the coating, blemish or soften thecoating, or react unfavorably with the substrate below the coating (suchas causing corrosion of metals). Silica also adds some opacity to thecoating since it has a significantly different refractive index thanmost binders.

Applicant had two earlier applications (U.S. Pat. No. 9,527,961 and US2016/009953) that described polyamide containing polymers andpolyurethane dispersions where a high percentage of the polyamide wastertiary polyamide derived from piperazine.

SUMMARY OF THE INVENTION

This invention relates to polymer containing polyamide and multipleurethane and/or multiple urea linkages dispersions in aqueous medium(e.g., water and optional water soluble organics) containing polyamidesfrom specific cyclic aliphatic or aromatic primary or secondary aminegroups that impart low gloss (high matte) finishes to coatings appliedfrom polymer dispersions in aqueous medium. These polyamides are usefulas segments in the binder of a coating, ink, or adhesive. Thesepolyamides may also be prepared separately from the primary polymericbinders (e.g., a second polymer), both being put in the form of adispersion in aqueous media. The polymer containing polyamide andmultiple urethane linkages and/or urea linkages can be blended with thesecond polymer before dispersion of the blend in aqueous medium. Or thepolymer with polyamide and multiple urethane and/or multiple urealinkages and the second polymer can each be separately dispersed inaqueous medium and then the dispersed particles from each in aqueousmedium can be blended together. Or these polymer with polyamide may bemade as a masterbatch, optionally with a second polymer and thatmasterbatch can be blended with one or more other polymer dispersions tocreate the binder for a coating, ink or adhesive. The polymer of thebinder can be thermoplastic, thermoset, or elastomeric and is generallya water-borne dispersions of those resins. The unique feature of thesepolymer dispersions with their specific polyamides is their ability toimpart a textured surface to a final coating or ink wherein saidtextured surface gives a decreased gloss (increases matting) of thecoating or ink finish. The amount of the polyamide in the polymers ofthe coating or ink affects the level of gloss reduction or mattingachieved.

DETAILED DESCRIPTION OF THE INVENTION

Definitions: We will use the parentheses to designate 1) that thesomething is optionally present such that monomer(s) means monomer ormonomers or (meth)acrylate means methacrylate or acrylate, 2) to qualifyor further define a previously mentioned term, or 3) to list narrowerembodiments.

The terms “hydrocarbyl” or “hydrocarbylene” denotes a group having acarbon atom directly attached to the remainder of the molecule andhaving a hydrocarbon or predominantly hydrocarbon character within thecontext of this invention. Such groups include purely hydrocarbongroups; that is, aliphatic, and optionally groups containingnon-hydrocarbon substituents (containing hetero atoms) which do notalter the predominantly hydrocarbon character of the group. Examples ofnon-hydrocarbon substituents include hydroxy, nitro, cyano (cyano groupattaches via C atom and so does the acyl), alkoxy, acyl groups, etc.Suitable hetero atoms will be apparent to those skilled in the art andinclude, for example, nitrogen, oxygen and sulphur.

A first portion of this invention is the generation of polyamidesegments from a cyclic aliphatic or aromatic primary or secondarydiamine type component reacted with some form of reactive carbonyl suchas carboxylic acid, often a dicarboxylic acid, hydroxycarboxylic acid orlactone from hydroxycarboxylic acid. In one preferred embodiment, bothnitrogen atoms are attached to the cyclic or aromatic ring with nointervening atoms between the nitrogen and the ring. This reaction ofthe amine with a carboxylic acid generates water as a byproduct (or inthe case of a lactone, a hydroxyl group) and amide linkages. Thepolyamide segment formation can be promoted by removing the waterbyproduct. Generally, a polyamide number average molecular weight fromabout 500 to 5,000 g/mole, more preferably from about 800 or 1000 to3000 g/mole has been easily processable into the final binder by thistechnology. Applicant is using polyamide to mean two or more amidelinkages in the oligomer or polymer. These polyamides may initially beamine, hydroxyl, or carboxylic acid terminated. Generally, it isdesirable to form hydroxyl end groups as these are conventional terminalgroups for precursors to polyurethanes.

Many of the examples use a slight excess of the diamine relative to themoles of reactive carbonyl and/or carboxylic functional groups and reactto a very low acid number, consuming substantially all of the availablecarboxylic groups. Adjusting the stoichiometry of reactive amine andacid groups can help control the molecular weight and the predominantterminal groups. In some embodiments, the only carboxylic acid group isa hydroxycarboxylic acid or lactone therefrom and this results in ahydroxyl terminated polyamide that forms a polyurethane when reactedwith a polyisocyanate.

In other embodiments, the amine repeating unit is first reacted with adicarboxylic acid to create an amine terminated polyamide and then thatpolyamide is chain extended with a lactone polymerization on the end ofthe amine terminated polyamide. Other reactants (e.g., trifunctionalamines or trifunctional carboxylic acids or monofunctional amines ormonofunctional carboxylic acids) or impurities can be included in thepolyamide formation provided that they are used in small amountsrelative to the required reactants and don't unduly increase or decreasethe molecular weights of the reaction products.

The preferred cyclic aliphatic or aromatic and primary or secondarydiamines reactants are the following Formulas Ib through IVb.

or combinations thereof

wherein R₁ to R₅ are independently selected from H or a C₁ to C₄ linearor branched alkyl group, and in one embodiment, desirably at least 80,90 or 95 wt. % of the total R₅ groups in the amine repeating units is H.

The preferred cyclic aliphatic or aromatic and primary or secondarydiamines repeating units are Formula I to IV.

or combinations thereof

wherein R₁ to R₅ are independently selected from H or a C₁ to C₄ linearor branched alkyl group, and in one embodiment, desirably at least 80,90 or 95 wt. % of the total R₅ groups in the amine repeating units is Hand at least 80, 90 or 95 wt. % of the cyclic aliphatic or aromaticportion of the molecule are cyclic aliphatic such that Formula I and II(preferred) become Formula Ia and Formula IIa as shown here:

wherein R₁ through R₄ are individually a H or a C₁ to C₄ alkyl group. Inone embodiment, at least 60, 70 or 80 of the R₁, R₂, R₃, and R₄ groupsof the diamine of Formulas Ib-IVb, Formulas I-IV, and Formulas Ia-IIaused to make the polyamide or the amine repeating units of the polyamideare hydrogen. In one embodiment, desirably at least 80, 90, 95, 99 or100 mole % of the R₅ groups are hydrogen resulting in primary diamines.These primary amines when reacted into a polyamide generate therepeating unit of

wherein R₁ to R₄ are as described above. Examples of the aliphaticprimary cyclic diamines include 1,3-diamino cyclohexyl and the4,4′-methylenebis(cyclohexylamine) optionally mono or dialkyl (methylpreferred) substituted as taught above. While cyclic aliphatic diaminesand cyclic aromatic diamines are shown, it is believed that the aromaticdiamines may generate yellow color in polymeric coatings and inks uponexposure to light sources. Thus, the primary aliphatic and/or secondarydiamines are slightly preferred.

The amount of primary and/or secondary diamine with particular aliphaticcyclic or aromatic structure of Formulas I-IV with the amine groupsattached directly to a carbon atom in the cyclic structure incorporatedas an amine compound backbone is from about 1 or 2 to about 20 or 25 wt.% of the total polymers in said polymer dispersion, more desirably from4 to 15, and preferably from 6 to 15 based on the total amount ofpolymer in the polyurethane dispersion (i.e., generally coating wt. lessaqueous phase, filler, and pigment wt.).

In one embodiment, the diacids reacted with the aliphatic cyclic diaminecomponent are C₄ to C_(50 or 60) dicarboxylic acids including C₁₀ to C₄₀dicarboxylic acids and dimer fatty acids. Particularly preferred largerdiacids include sebacic acid, dodecanedoic acid and dimer acids. Therepeat unit from them would have the structure

wherein Ra is a hydrocarbyl group of C₂ to C_(48 or 58) more preferableof C₈ to C₃₈. Preferred diacids include sebacic acids and C₁₀ to C₄₀aliphatic diacids. Dimer and trimer fatty acids are very useful in thisapplication.

The terms dimer fatty acids (also referred to as dimer diacids or dimerfatty diacid) and trimer fatty acids are well known in the art, andrefers to the dimerization or timerization products of mono- orpolyunsaturated fatty acids and/or esters thereof. They are prepared bypolymerizing fatty acids under pressure, and then removing most of theunreacted fatty acid starting materials by distillation. The finalproduct usually contains some small amounts of mono fatty acid andtrimer fatty acids, but is mostly made up of dimer fatty acids.

The dimer and trimer fatty acids used in the present invention arepreferably derived from the dimerization products of C₁₀ to C₃₀ fattyacids, more preferably C₁₂ to C₂₄ fatty acids, particularly C₁₄ to C₂₂fatty acids, further preferably C₁₆ to C₂₀ fatty acids, and especiallyC₁₈ fatty acids. Thus, the resulting dimer fatty acids preferablycomprise carbon atoms per molecule in the range from 20 to 60, morepreferably 24 to 48, particularly 28 to 44, further preferably 32 to 42,and especially 36 carbon atoms. Preferably, the fatty acids startingmaterials used to make the dimer are linear monounsaturated fatty acids.

The molecular weight (weight average) of the dimer fatty acid ispreferably in the range from 450 to 690, more preferably 500 to 640,particularly 530 to 610, and especially 550 to 590 g/mole. The molecularweight (weight average) of the trimer fatty acids is preferably in therange from 750 to 950, more preferably 790 to 910, particularly 810 to890, and especially 830 to 870. In addition to the dimer fatty acids,dimerization usually results in varying amounts of trimer fatty acids(so-called “trimer”), oligomeric fatty acids, and residues of monomericfatty acids (so-called “monomer”), or esters thereof, being present.They are available from Croda under the Pripol™ trademark or ArizonaChemical under the Unidyme™ trademark.

The dimer fatty acid used in the present invention preferably may have adimer fatty acid (or dimer) content of greater than 60 wt. %, morepreferably greater than 70 wt. %, particularly greater than 80 wt. %,and especially greater than 85 w %. In addition, particularly preferreddimer fatty acids may have a trimer fatty acid (or trimer) content ofless than 40 wt. %, more preferably less than 30 wt. %, particularlyless than 20 wt. %, and especially less than 15 wt. %. Furthermore, thedimer and or trimer fatty acid preferably comprises less than 10 wt. %,more preferably less than 6 wt. %, particularly less than 4 wt. %, andespecially less than 3.5 wt. % of mono fatty monoacid (or monomer). Allof the above weight percentage values are based on the total weight ofpolymerized fatty acids and mono fatty acids present.

Preferred hydroxycarboxylic acids with the formula HO—C(═O)—R_(f)—O—Hand cyclic lactones therefrom of the formula

include linear, branched and cyclic R_(f) structures with the aboveformula-with 2 to 15 carbon atoms, more preferably 2 to 5 carbon atoms(where R_(f) has from 1 to 14 carbon atoms, more preferably 1 to 4carbon atoms). Various nonsubstituted and alkyl substitutedcaprolactones and valerolactones are preferred. Both thehydroxycarboxylic acid and the lactones therefrom result in a repeatingunit of the structure —(C(═O)—R_(f)—O—)— with the generation of one moleof water, if starting with hydroxycarboxylic acid.

As indicated in the summary of the invention the hydroxycarboxylic acidor lactones therefrom can be used with or without the dicarboxylic acids(and vice versa) to generate amide linkages and using the lactone orhydroxycarboxylic acid to chain extend polyamides of the invention withpolyester repeating units. When the polyamide is chain extended withpolyester repeating units from the hydroxycarboxylic acid or lactonestherefrom, the amount of polyester repeating units is desirably fromabout 1 to about 75 wt. % of the polymer of the polyurethane dispersion.

The polyamide repeating structure of one mole of diacid and one mole ofthe specified primary diamine would look like

wherein the primary diamine component would look like

and the R_(b) of the diamine would look like the structure selected fromthe group of

wherein R₁ through R₄ are as described above. If the amine repeatingunit was of the secondary amine type with a non-hydrogen R₅ group, thestructure would have the R₅ group on the nitrogen of the amide linkages.These repeating units would be the most common in the polyamide, butthere could be monofunctional amide forming reactants or trifunctionalamide forming reactants present, provided that at least 50, 70, 80, 90or 95 mole percent of the amine reactants were difunctional.

A second embodiment of the invention is a) incorporating or blending asecond, third or more polymer(s) into a) the polymer containingpolyamide and multiple urethane linkages and/or multiple urea linkagesto be dispersed into aqueous medium, or b) making separate dispersionsof the polymer containing polyamide and multiple urethane and/ormultiple urea linkages and a second, third or more polymer(s) in aqueousmedium that are then blended as dispersions to form a blend. These twoprocedures are desirable as the amount of the polymer containingpolyamide and multiple urethane linkages and/or multiple urea linkageswith repeating units of the Formulas I to IV controls the relativeamount of matting or gloss reduction in the final film of the polymer.Blending two polymers, one with the polyamide having repeating units ofFormulas I to IV with a polymer(s) that substantially lack repeatingunits of Formulas I to IV, allows control of the level of matting orgloss reduction. Combinations of a) and b) can be used where one secondpolymer is blended with the polymer containing polyamide and multipleurethane and/or multiple urea linkages prior to dispersion in aqueousmedium and a third polymer is made into a separate dispersion in aqueousmedium and later blend with the polymer containing polyamide andmultiple urethane and/or multiple urea linkages and second polymer thatwere blended before dispersion in aqueous medium. We generally use theterm incorporating when talking about polymer segments in thepolyurethane to mean covalently bonded into the polyurethane. Wegenerally use the term blended to mean forming a physical blend.

A variation of the above embodiment of the invention (optionally used incombination) includes the option of incorporating the polymer containingpolyamide and multiple urethane and/or multiple urea linkages into alarger polyurethane structure by polymerizing an a) ester formingmonomer(s) and/or b) other polyamide forming monomer(s) onto thepolyamide chain ends or coupling the polyamide to other large oligomeror polymeric species such as with reactions of Zerewitinoff reactivegroups on the oligomeric or polymeric species with polyisocyanates.

In one embodiment, a polyester segment is added via ester polymerizationto one or both ends of the polyamide polymer. This may be accomplishedby adding polyester forming monomer(s) to the polyamide, optionallycatalyzing the ester polymerization, and stirring and heating thereactants. In one embodiment poly (caprolactone) can be added via esterpolymerization to one or both ends of the polyamide. The molecularweight of the polyester segments can be controlled by the amount ofpolyester forming reactants added relative to the number of polyamidesegments and the reaction conditions. Alternatively, dicarboxylic acidand dihydroxyl compounds can be polymerized in the presence of thepolyamide and partially or fully coupled to said polyamide byconventional condensation polymerization.

Alternatively from polymerizing a different polymer structure directlyfrom the monomer(s) onto or with said polyamide, one can usepolyisocyanate reactants to couple said polyamide from cyclic aliphaticor aromatic and primary or secondary polyamines to other monomers, oroligomeric or polymeric species. For example, polyester, polyether, orpolycarbonate segments having about two terminal Zerewitinoff groups persegments can be coupled with polyisocyanates onto the polyamide segmentsthat provide matting. The polyether, polyester, polycarbonate segmentsdesirably have about two Zerewitinoff groups per segment as this isthought to result in linear polymers when the polyisocyanate has abouttwo reactive isocyanate groups per polyisocyanate. It is known that alittle monofunctional reactant or trifunctional reactant can be used andthe results are similar (especially if the amount of monofunctional andtrifunctional reactants are about equal in moles such that the averagefunctionality remains about 2). However, if too much monofunctional ortrifunctional reactants are used, the product can be too low or too highof molecular weight. Zerewitinoff groups are well known and are definedas active hydrogen containing groups (such as amine or hydroxyl, whichare the primary Zerewitinoff groups of this disclosure) that arereactive with isocyanates to form covalent chemical bonds called urea orurethane linkages. The bond is between a hydroxyl and isocyanate groupwhen a urethane linkage is formed and if the bond is between an aminegroup and an isocyanate group, then a urea linkage is formed. In onepreferred embodiment, the polyester, polyether, polycarbonate segmentswith Zerewitinoff terminal groups have a number average molecular weightfrom about 500 to about 5,000 g/mole.

This number average molecular weight can be calculated if the polyester,polyether, polycarbonate is difunctional and one knows the number andtype of functional groups per polymer segment by simply dividing thegrams of segments in the sample by (0.5 times the number of functionalgroups in moles in the sample). This number average molecular weight canalso be determined by gel permeation chromatography (gpc) in a goodsolvent like tetrahydrofuran and calibrating the gpc columns with aseries of commercially available known molecular polystyrene calibrationsamples. Generally, the two methods give very similar molecular weights.

A series of polyamide oligomers from conventional difunctional acids andcycloaliphatic primary diamines were made. The initial oligomers maycomprise amine terminal groups, carboxyl terminal groups, or otherterminal groups derived from reacting the terminal amine or carboxylgroups with other reactants. The presence of strong hydrogen bond inthese structures makes them less deformable during film formation, andwhile not wishing to be bound by theory, seems to facilitate formationof the desired textured coating surfaces with high matt/low glossfinishes when the films form from the aqueous dispersions. This occurseven at low molecular-weight for the polyamide from the particularaliphatic or aromatic cyclic primary or secondary diamines.

Many of the oligomers, telechelics, and polymers of this specificationare made by condensation reactions of reactive groups on desiredmonocarboxylic acid or dicarboxylic acid monomers and the cycloaliphaticand/or aromatic primary or secondary diamine monomer(s). Triaminemonomers and tricarboxylic acids are less desirable for this as they arethought to produce highly branched less deformable polyamides. Thesecondensation reactions between carboxylic acid groups and amine orhydroxyl groups are well known and are driven by the removal of waterand or catalysts. The formation of amides from the reaction ofcarboxylic acid groups and amine groups can be catalyzed by boric acid,boric acid esters, boranes, phosphorous acid, phosphates, phosphateesters, amines, acids, bases, silicates, and silsesquioxanes. Additionalcatalysts, conditions, etc. are available in textbooks such as“Comprehensive Organic Transformations” by Larock.

Two earlier applications (U.S. Pat. No. 9,527,961 and US 2016/0009953)described tertiary polyamide containing polymers and polyurethanedispersions where a high percentage of the amide linkages were tertiaryamide linkages derived from piperazine and other secondary diamines.These polymers were not self-matting or low gloss in coatingapplications. In one embodiment of this disclosure, it is desirable toblend (prior to or after dispersing in aqueous medium) or mutuallyincorporate the matting polymer containing polyamide and multipleurethane linkages and/or multiple urea linkages of this disclosure withthose earlier tertiary polyamide containing polymers. This would impartvariable levels of flatting or gloss reduction into those polyamides. Inone embodiment, it is desirable to include 5-85 wt. %, more desirably atleast 10, 15, 20 or 25 wt. % and up to about 65 wt. % of polyamides(based on the combined weight of the polymer(s) in the polyamidecontaining polyurethane dispersion in aqueous medium) where thepolyamides are characterized as at least 75 wt. % amide repeat units andat least 60, 75 or 80 mole % of the amide linkages are tertiary amidelinkages and at least 60, 70 or 80 wt. % of the amine groups in theamide repeat units are based on cyclic diamines where the nitrogen atomsare part of the ring and having 3 or 4 to 10 carbon atoms such aspiperazine or a mono or dialkyl (C₁-C₄) substituted piperazine.

The tertiary polyamides of those earlier disclosures had lower minimumfilm formation temperature (generally from about −10 to about 20, 25 or30° C.) than most polyamides from primary amines, such that they couldform films at or near room temperature (about 20-25° C.) without a lotof plasticizer, solvent, or coalescing agents). The tertiary amidelinkage of those disclosures were formed from the covalent bond betweena secondary amine and a carboxylic acid group resulting in a tertiaryamide linkage (an important aspect of those earlier disclosures to getlower minimum film formation temperature). Primary amines react withcarboxylic acid type groups to form secondary amides, which generallyhave higher minimum film formation temperatures, other factors beingheld the same.

Sometimes it is desirable to convert a carboxylic acid terminatedpolyamide segment to a hydroxyl (Zerewitinoff group) by reacting with anaminoalcohol, such as N-methylaminoethanol or HN(R^(α))(R^(β)) whereR^(α) is a C₁ to C₄ alkyl group and R^(β) comprises an alcohol group anda C₂ to C₁₂ alkylene group, alternatively R^(α) and R^(β) can beinterconnected to form a C₃ to C₁₆ alkylene group including a cyclicstructure and pendant hydroxyl group (such as in 2-hydroxymethylpiperidine), either of which can create a polyamide with terminalhydroxyl groups. The reaction of the secondary amine (as opposed to thehydroxyl group) with the carboxylic acid can be favored by using a 100%molar excess of the amino alcohol and conducting the reaction at 160°C.+/−10 or 20° C. The excess amino alcohol can be removed bydistillation after reaction.

In one embodiment the polymer containing polyamide and multiple urethaneand/or multiple urea linkages dispersions are copolymerized with orblended with other polyamide containing polymer dispersions (describedas earlier tertiary polyamides) such as described in the next couple ofparagraphs. Preferred dicarboxylic acids for forming the earliertertiary polyamides are where the alkylene portion of the dicarboxylicacid is a cyclic, linear, or branched (optionally including aromaticgroups) alkylene of 2 to 36 carbon atoms, optionally including up to 1heteroatom per 3 or 10 carbon atoms, more preferably from 4, 8 or 12 to36 carbon atoms (the diacid would include 2 more carbon atoms than thealkylene portion). These include dimer fatty acids, hydrogenated dimeracid, sebacic acid, etc. Generally, we prefer diacids with largeralkylene groups as this generally provides polyamide repeat units withlower minimum film formation temperatures.

Preferred diamines for forming the tertiary polyamides include thosewith from 6 to 60 carbon atoms, more desirably 6 to 20, and preferably 6or 12, or 13 to 15, 17 or 20 carbon atoms, optionally including 1heteroatom (besides the two nitrogen atoms) for each 3 or 10 carbonatoms of the diamine and optionally including a variety of cyclic,aromatic or heterocyclic groups providing that one or both of the aminegroups are primary amines, a preferred formula is

and a R_(b) is a direct bond or a linear or branched (optionally beingor including cyclic, heterocyclic, or aromatic portion(s)) alkylenegroup (optionally containing up to 1 or 3 heteroatoms per 10 carbonatoms of the diamine) of 2 to 36 carbon atoms and more preferably 2 or 4to 12 carbon atoms and R_(c) and R_(d) are individually a linear orbranched alkyl group of 1 to 8 carbon atoms, more preferably 1 or 2 to 4carbon atoms or optionally R_(c) and R_(d) connect together to form asingle linear or branched alkylene group of 1 to 8 carbon atoms oroptionally with one of R_(c) and R_(d) is connected to R_(b) at a carbonatom, and more desirably where R_(c) and R_(d) connect together andcombined are from 1 or 2 to 4 carbon atoms.

In one embodiment of the prior disclosures about tertiary polyamides,desirably at least 50 wt. %, more desirably at least 60, 70, 80 or 90wt. % of said polyamide oligomer or telechelic polyamide comprise repeatunits from diacids and diamines of the structure of the repeat unitbeing

wherein R_(a) is the alkylene portion of the dicarboxylic acid and is acyclic, linear, or branched (optionally including aromatic groups)alkylene of 2 to 36 carbon atoms, optionally including up to 1heteroatom per 3 or 10 carbon atoms of the diacid, more preferably from4 to 36 carbon atoms (the diacid version would include 2 more carbonatoms than the alkylene portion of the diacid) and

wherein R_(b) is according to the formula

wherein R_(b) is from 2 to 36 or 60 carbon atoms and more preferably 2or 4 to 12 carbon atoms and R_(c) and R_(d) are individually a linear orbranched alkyl group of 1 to 8 carbon atoms, more preferably 1 or 2 to 4carbon atoms or R_(c) and R_(d) connect together to form a single linearor branched alkylene group of 1 to 8 carbon atoms or optionally with oneof R_(c) and R_(d) is connected to R_(b) at a carbon atom, and moredesirably R_(c) and R_(d) being connected together and being an alkylenegroup of 1 or 2 to 4 carbon atoms.

During the reaction of the polyamides of this disclosure with thepolyisocyanates to form the polyamide containing polyurethane, one canhave other species present with Zerewitinoff groups to co-react into theresulting polyurethane. These can be low molecular weight species (e.g.,less than 500 g/mole diols or diamines) or higher molecular weightspecies (e.g., 500 to 5,000 g/mole oligomers that are added to form thehigh or low Tg phases in the resulting urethane polymer). Generally, ifone wants a low viscosity prepolymer to make a polymer dispersion inaqueous medium, one only reacts the components with a stoichiometryimbalance between the reactive groups to create moderate molecularweight species called a prepolymer with the functional group present inexcess being the dominant terminus of most prepolymer units. This isusually accomplished by keeping the stoichiometry of the isocyanategroups to Zerewitinoff groups away from the 1:1 ratio (such thatprepolymers of limited molecular weight are produced because of theexcess of isocyanate or Zerewitinoff groups that serve as terminalgroups). The molecular weight of the prepolymer is kept fairly low(5,000 g/mole to 100,000 g/mole) so that the prepolymer is a liquid atroom temperature or slightly above room temperature (generally up toabout 80° C.). This low viscosity at 80° C. or below facilitates mixingand shearing of the liquid prepolymer into a finely dispersed colloidalprepolymer phase stable in water. Often, an excess of isocyanate groupsare used so that the prepolymer is isocyanate terminated.

The molecular weight of the urethane prepolymer can be increased (or itis sometimes referred to as chain extending the prepolymer into aurethane polymer) after the dispersion of prepolymer is made. This canbe done by adding to the dispersion low molecular weight species such asdiols, triols, tetrols, or diamines, triamines or tetraamines that canreact with isocyanate terminated prepolymers linking them into highermolecular weight species. Isocyanate groups on the prepolymer can alsoreact with water from the continuous phase to generate CO₂ gas andterminal amine groups on some of the prepolymer. The amine groups onsome of the prepolymer can then react with isocyanate groups on otherprepolymers and chain extend both species. While the followingparagraphs describe dispersing groups that can be incorporated into theprepolymer/polymer, it is also possible to utilize dispersants andsurfactants of the anionic, cationic, nonionic, or zwitterionic type ormixtures thereof to facilitate the dispersion of the prepolymer/polymerin a continuous media.

Surface active dispersing species such as anionic, cationic, nonionic,or zwitterionic species are desirably added to the prepolymer (orpolymer) if it is desired to disperse the prepolymer (or polymer) in acontinuous aqueous phase. These dispersing species help to providecolloidal stabilization to the dispersed phase. If surface activedispersing groups are to be incorporated into the polymer, it isdesirable to include them in the reaction of the polyamide oligomer orother sources of Zerewitinoff reactive groups (e.g., during the urethaneprepolymer preparation). Dispersing groups that have Zerewitinoff activegroups, which react with isocyanate groups to form urea or urethanelinkages, are particularly preferred for this purpose.

If one wants to form a polyurethane dispersion in aqueous medium, it isdesirable to include a water dispersing component either as asurfactant/emulsifier or as a water dispersing group that can beincorporated into the polyurethane itself. Therefore it is oftendesirable to include at least one water-dispersibility enhancingcompound, i.e., a monomer with a dispersing functionality, which has atleast one, hydrophilic, ionic or potentially ionic group in thereactants for the urethane forming polymers and prepolymers of thisinvention to assist dispersion of the polymer/prepolymer in aqueousmedium. Typically, this is done by incorporating (via one or twoZerewitinoff groups on the compound) a compound bearing at least onehydrophilic group or a group that can be made hydrophilic, e.g., bychemical modifications such as neutralization, into thepolymer/prepolymer chain. These compounds may be of a nonionic, anionic,cationic or zwitterionic nature or the combination thereof. For example,anionic groups such as carboxylic acid groups can be incorporated intothe prepolymer and subsequently ionized by a salt-forming compound, suchas ammonium hydroxide or a tertiary amine defined more fullyhereinafter. Anionically dispersible urethane prepolymers/polyurethanesbased on carboxylic acid groups generally have an acid number from about1 to about 60 mgKOH/gram, typically 1 to about 40, or even 10 to 35 or12 to 30 or 14 to 25 mg KOH/gram. Other water-dispersibility enhancingcompounds can also be reacted into the urethane prepolymer backbonethrough urethane linkages or urea linkages, including lateral orterminal hydrophilic ethylene oxide or ureido units.

Water dispersibility enhancing compounds of particular interest arethose which can incorporate weak carboxyl groups into the prepolymer.Normally, they are derived from hydroxy-carboxylic acids having thegeneral formula (HO)_(x)Q(COOH)_(y), wherein Q is a straight or branchedhydrocarbon radical containing 1 to 12 carbon atoms, and x and y are 1to 3. Examples of such hydroxy-carboxylic acids include dimethylolpropanoic acid, dimethylol butanoic acid, citric acid, tartaric acid,glycolic acid, lactic acid, malic acid, dihydroxymalic acid,dihydroxytartaric acid, and the like, and mixtures thereof.Dihydroxy-carboxylic acids are more preferred with dimethylol propanoicacid and dimethylol butanoic acid being most preferred.

Another group of water-dispersibility enhancing compounds of particularinterest are side chain hydrophilic monomers. Some examples includealkylene oxide polymers and copolymers in which the alkylene oxidegroups have from 2-10 carbon atoms as shown, for example, in U.S. Pat.No. 6,897,281, the disclosure of which is incorporated herein byreference. There are commercially available polyethers with two terminalhydroxyl groups near one end of the polyether that can be incorporatedas nonionic dispersing moieties into urethanes and urethane prepolymers.These have a significant portion of the polyether extending in atethered fashion from those two points of attachment to the urethane atone end the polyether. These include Tegomer® D3403 used in U.S. Pat.No. 6,897,381 and Ymer™ N-120 from Perstop.

Water dispersibility enhancing compounds can impart cationic nature ontopolyurethane. Cationic polyurethanes contain cationic centers built intoor attached to the backbone. Such cationic centers include ammonium,phosphonium and sulfonium groups. These groups can be polymerized intothe backbone in the ionic form or, optionally, they can be generated bypost-neutralization or post-quaternization of corresponding nitrogen,phosphorous, or sulfur moieties. The combination of all of the abovegroups can be used as well as their combination with nonionicstabilization. Examples of amines include N-methyldiethanol amine andaminoalcohols available from Huntsman under Jeffcat® trade name such asDPA, ZF-10, Z-110, ZR-50 and alike. They can make salts with virtuallyany acid. Examples of acid include hydrochloric, sulfuric, acetic,phosphoric, nitric, perchloric, citric, tartaric, chloroacetic, acrylic,methacrylic, itaconic, maleic acids, 2-carboxyethyl acrylate and other.Quaternizing agents include methyl chloride, ethyl chloride, alkylhalides, benzyl chloride, methyl bromide, ethyl bromide, benzyl bromide,dimethyl sulfate, diethyl sulfate, chloroacetic, acids and alike.Examples of quaternized diols include dimethyldiethanolammonium chlorideand N,N-dimethyl-bis(hydroxyethyl) quaternary ammonium methanesulfonate.

Other suitable water-dispersibility enhancing compounds includethioglycolic acid, 2,6-dihydroxybenzoic acid, sulfoisophthalic acid,polyethylene glycol, and the like, and mixtures thereof.

Although the use of water-dispersibility enhancing compounds ispreferred, dispersions of the present inventions can be prepared withoutthem by using high-shear dispersing methods and stabilizing bysurfactants.

Polyisocyanate

Suitable polyisocyanates have an average of about two or more isocyanategroups, preferably an average of about two to about four isocyanategroups per molecule and include aliphatic, cycloaliphatic, araliphatic,aromatic, and heterocyclic polyisocyanates, as well as products of theiroligomerization, used alone or in mixtures of two or more. Diisocyanatesare more preferred. Polyisocyanates can have the formulaR_(Q)—[N═C═O]_(z) wherein R_(Q) is a hydrocarbylene group of from 5 to20 carbon atoms, optionally including one or more cyclic aliphaticstructure or one or more aromatic ring and Z is from 1 to 4 moredesirably from 1 to 3 and preferably on average are predominately 2.

Specific examples of suitable aliphatic polyisocyanates include alpha,omega-alkylene diisocyanates having from 5 to 20 carbon atoms, such ashexamethylene-1,6-diisocyanate, 1,12-dodecane diisocyanate,2,2,4-trimethyl-hexamethylene diisocyanate,2,4,4-trimethyl-hexamethylene diisocyanate, 2-methyl-1,5-pentamethylenediisocyanate, and the like. Polyisocyanates having fewer than 5 carbonatoms can be used but are less preferred because of their highvolatility and toxicity. Preferred aliphatic polyisocyanates includehexamethylene-1,6-diisocyanate,2,2,4-trimethyl-hexamethylene-diisocyanate, and2,4,4-trimethyl-hexamethylene diisocyanate.

Specific examples of suitable cycloaliphatic polyisocyanates includedicyclohexylmethane diisocyanate, (commercially available as Desmodur™ Wfrom Bayer Corporation), isophorone diisocyanate, 1,4-cyclohexanediisocyanate, 1,3-bis-(isocyanatomethyl) cyclohexane, and the like.Preferred cycloaliphatic polyisocyanates include dicyclohexylmethanediisocyanate and isophorone diisocyanate.

Specific examples of suitable araliphatic polyisocyanates includem-tetramethyl xylylene diisocyanate, p-tetramethyl xylylenediisocyanate, 1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate, andthe like. A preferred araliphatic polyisocyanate is tetramethyl xylylenediisocyanate.

Examples of suitable aromatic polyisocyanates include4,4′-diphenylmethylene diisocyanate, toluene diisocyanate, theirisomers, naphthalene diisocyanate, and the like. Preferred aromaticpolyisocyanates include 4,4′-diphenylmethylene diisocyanate and toluenediisocyanate.

Examples of suitable heterocyclic isocyanates include5,5′-methylenebisfurfuryl

Conventional Blends with Other Polymers

The polymer containing polyamide and multiple urethane and/or multipleurea linkages formed into a dispersions of this invention can becombined with compatible polymers (i.e., a second polymer) and/orpolymer dispersions by methods well known to those skilled in the art.Generally the second polymer can be distinguished from the polymercontaining polyamide and multiple urethane and/or urea linkages of thedispersion because it will not be covalently bonded into said polymercontaining polyamide and multiple urethane and/or multiple urea linkagesand/or it will have less than the specified amounts of amine repeatingunits of Formula I and/or II that define the unique polymer of thisdisclosure. Such polymers, polymer solutions, and dispersions includethose described in A. S. Teot. “Resins, Water-Soluble” in: Kirk-OthmerEncyclopedia of Chemical Technology. John Wiley & Sons. 3rd Edn., Vol.20, H. F. Mark et al. Eds., pp. 207-230 (1982).

Composite Polymer Compositions (e.g., Polyurea/Urethane with FreeRadically Polymerizable Monomers) Providing Better Interpenetration ofPhases

In one embodiment, one can use ethylenically unsaturated monomer(s) as asolvent to reduce the viscosity of the prepolymer during preparation anddispersion of the prepolymer or polymer containing polyamide andmultiple urethane and/or multiple urea linkages and subsequentlypolymerize the unsaturated monomer(s) to form a polymer. Ethylenicallyunsaturated monomers and other free radically polymerizable monomers canbe polymerized by conventional free radical sources to form a polymerwithin the polymer containing polyamide and multiple urethane and/ormultiple urea linkages particle to form a composite polymer with thepolymer containing polyamide and multiple urethane and/or multiple urealinkages of the dispersion. Vinyl polymers is a generic term forpolymers derived from substantial portions of unsaturated monomers orpolymers derived from those monomers. Acrylic, often considered a subsetof vinyl, will refer to acrylic acid, acrylates, being esters of acrylicacid, and alkacrylates, such as methacrylates and ethacrylates, andpolymers therefrom. Various styrene and alkyl substituted styrene typemonomers, including divinyl benzene, (meth)acrylonitrile, vinyl esterssuch as vinyl acetate, unsaturated amides such as acrylamides, dienes of4 to 6 carbon atoms, vinyl monomers with dispersing moieties thereonsuch as AMPS monomer (2-acrylamido-2-methylpropane sulfonic acid) andother vinyl monomers readily copolymerize with acrylic monomers.Additional free-radically polymerizable material, e.g., otherunsaturated monomers, may be added to the vinyl or acrylic monomers tocopolymerize. These other monomers can be monomers that technically arenot ethylenically unsaturated such as maleic anhydride, maleic acid, andother monomers where the carbon-carbon double bond is nearly as reactive(and copolymerizable with) as a ethylenically unsaturated monomers.Dienes are considered ethylenically unsaturated and copolymerize withboth the broad category of vinyl monomers and narrow category of acrylicmonomers.

The polymerization within the polyurethane particles can be done byforming the aqueous dispersions of polymer containing polyamide andmultiple urethane and/or urea linkages composite and then polymerizingadditional monomers by emulsion or suspension polymerization in thepresence of these dispersions. Another way of making composite polymersis to include ethylenically unsaturated monomers in the polymercontaining polyamide and multiple urethane and/or urea linkages inprepolymer form, e.g., either with the reactants to form the prepolymerand/or any time before the polyurethane prepolymer is dispersed, andcause these monomer to polymerize before, during and/or after theprepolymer is dispersed in aqueous medium. In one embodiment, the weightpercent of polymer(s) from free radically polymerizable monomers (orpolymer therefrom) based on 100 parts of combined polymer containingpolyamide and multiple urethane and/or multiple urea linkages and freeradically polymerizable monomers and any additional blended orincorporated polymers will be at least 1, 5, or 10 weight percent anddesirably up to 30, 40 or 50 weight percent of the combined polymers inthe polymer containing polyamide and multiple urethane and/or multipleurea linkages dispersion.

In one approach, the free radically polymerizable monomers(ethylenically unsaturated monomers) act as a diluent (or plasticizer)during prepolymer formation. Composites of polymer containing polyamideand multiple urethane and/or multiple urea linkages of this inventionwith and without free radically polymerizable monomers (e.g., acrylics)or their polymer can be made by any of these approaches.

Broadened Definition of Composite and/or Hybrid Polymer in Dispersion inAqueous Medium

Composites (also known as hybrid compositions) can allow one to adjustthe weight percentage of polyamide repeat units relative to other repeatunits (e.g., optionally polyether, polycarbonate, polyester segments,polysiloxane, etc.) in the polymer containing polyamide and multipleurethane and/or urea linkages to optimize the matting effect or glossreadings. Thus this technology provides several ways to independentlycontrol the amount of polyamide in the composite polyurethane particles,which can have effects on the polarity or hydrogen bonding of thecomposite particles, the surface tension of the composite particles,and/or the modulus, tensile strength, etc. of the composite polymer at aparticular key temperature.

By the term composite and/or hybrid, we intend to include a variety ofmixtures of other polymers with a polyamide rich polymer type, such as apolymer containing polyamide and multiple urethane and/or multiple urealinkages. The polymers that contain polyamide segments may have othercomonomers or comonomer segments linked directly or indirectly to thepolyamide segments. These comonomers can include things like polyethers,polyesters, polycarbonates, polysiloxanes, etc. The composite and/orhybrid polymers of the composite and/or hybrid dispersions haveapproximately the same particle size ranges as disclosed forpolyurethane dispersions in water.

The composite and/or hybrid polymer dispersions may have within thepolymer anionic, nonionic, or zwitterionic colloidal stabilizing groupsas earlier disclosed.

Water can be present in amounts from about 10, 20 or 30 weight percentto about 70, 80 or 90 wt. % of the polymer containing polyamide andmultiple urethane and/or urea linkages in the form of a dispersion inaqueous media. Typically, lower water content saves on shipping costsfor the same amount of polymer but viscosity of the dispersions tend torise when the water content is minimized.

In one embodiment, it is desirable that the polymer containing polyamideand multiple urethane and/or multiple urea linkages or one of the secondor third polymers therein be partially crosslinked to increase thephysical properties of the polymer such as tensile strength and modulus.This can be achieved by adding a variety of crosslinking functionalityto polymers in the dispersion or adding a separate crosslinkingcomponent to polymer containing polyamide and multiple urethane and/ormultiple urea linkages in the form of a dispersion. The crosslinkingcomponents can include polyisocyanate, blocked polyisocyanate,aziridines, ketone-hydrazine crosslinking, etc. The polyisocyanates,blocked polyisocyanate, and ketone-hydrazine crosslinking are eachpreferred types.

Reactive crosslinking moieties of the blocked isocyanate (e.g., MEKO) or1,3-dicarbonyl compound type (e.g., DEM) allow for delivery of atwo-component performance by a one-component system. Several types ofcompounds can be employed as blocking (a.k.a. protecting or masking)agents to provide crosslinking functionality to the urethane polymer andcoating composition. Their function is to temporarily protect isocyanategroups from undesired reactions. The main requirement for the blockingcompound is for its reaction with isocyanate to be reversible. When thereaction is reversed, the isocyanate group is regenerated and isavailable for further reactions after deblocking. The deblockingreaction can be triggered by physical or chemical means, for example, byelevated temperatures, radiation, vacuum, catalysts, compounds withactive hydrogen, or combinations thereof. Malonates (such as DEM) are avariation on blocking compounds as they do block isocyanate groups fromundesirable reactions such as with water, but when combined withhydroxyl-containing substrates, rather than deblock at highertemperatures during crosslinking, they react at lower temperatures toform a chemical bond with such reactive hydroxyls.

Examples of reactive crosslinking moieties (including blocking agents)include 1,3-dicarbonyl compounds, oximes and other N-hydroxyl compounds,phenols, alcohols, lactams, imidazoles, pyrazoles, acids, mercaptanes,imides, secondary amines, cyanoacetates, malononitrile and itsderivatives, and sulfites. The preferred reactive crosslinking agent(including blocking agents) are 1,3-dicarbonyl compounds(dicarbonylmethanes) (U.S. Pat. No. 2,826,526). Examples include acetylacetone and its derivatives, alkyl acetoacetates, alkoxyalkylacetoacetates, barbituric acid and its derivatives. The reactivecrosslinking moiety may be reacted into the prepolymer and thereafterthe polyurethane or it can be a separate isocyanate basedcompound/moiety (e.g., blocked polyisocyanate moiety or reaction productof a polyisocyanate and a 1,3-dicarbonyl compound) that reacts tocrosslink the polyurethane or bind the polyurethane to a substrate.

Oximes are another group of generally preferred blocking agents. Oximescan be represented by a general formula CRR′═NOH, where R and R′ mayindependently be H or C_(n)H_(2n+1). R and R′ may also containcycloaliphatic, aromatic groups, and groups with heteroatoms includingheterocyclic groups. The oxime may be an aldoxime when one or both R andR′ are hydrogen, or ketoxime when both R and R′ are hydrocarbyl groupsdesirably alkyl groups having from 1 to 12 carbon atoms. Examples ofaldoximes include formaldoxime, acetaldoxime, propionaldoxime,butyraldoxime, benzaldoxime and the like. Examples of ketoximes includeacetoxime, butanone oxime, methyl ethyl ketoxime (MEKO), methyl isobutylketoxime, cyclopentanoneoxime, cyclohexanone oxime, acetophenone oximeand the like. 1,3-Dicarbonyl compounds and oximes can be used alone orin combination. They can be partially replaced by other blocking agents.

Other blocking agents include lactams, secondary and tertiary alcohols,phenols, pyrazoles, mercaptans, N-hydroxyl compounds and their mixtures.Some specific examples of other suitable blocking agents includetriazole, tetrazole, imidazole, caprolactam, phenol and its derivativessuch as esters of hydroxybenzoic acids, pyrazole, 3,5-dimethylpyrazole,dibutylamine, diisopropylamine, piperidine, piperazine, tert-butanol,cyclohexanol, isopropanol, glycerine carbonate, N-hydroxysuccinimide,hydroxypyridine, and esters of hydroxamic acid. Combinations of two ormore blocking agents are preferred if a stepwise reaction is desired,particularly mixtures of blocking agents which deblock at differenttemperatures.

The isocyanate blocking reaction can be performed at virtually any stageof the PUD synthesis and is usually carried out at temperatures above30° C. The reaction times vary and depend on temperature and type andconcentration of isocyanate, blocking agent and other ingredients. Theblocking reaction can be accelerated by the use of a catalyst. Suitablecatalysts include Brönsted base and/or Lewis acid. Examples include thealkali metal alcoholates and phenolates and metal carboxylates.

The deblocking may occur during chain extension or during polymer dryingand/or during a separate curing. Often, it is preferred to use ablocking agent, which will evaporate from the polymer during drying orcuring. In these cases, low molecular weight blocking agents such asdimethyl malonate, diethyl malonate, acetoxime, butanone oxime,butyraldoxime and the like are preferred.

Blocked isocyanates of the present invention may also be used incombination with other crosslinking chemistries such as summarized in“Functional Latex and Thermoset Latex Films” J. W. Taylor M. A. WinnikJ. Coatings Tech., Research, v. 1, No. 3, p. 163 (2004) which isincorporated here by reference. These include melamine-basedcrosslinkers, metal carboxylates, aziridines, carbodiimides, epoxides,unsaturated compounds, acetoacetoxy- and ketone-functional polymers andadditives, enamine and amine crosslinking, isocyanates and self-blockedisocyanates, OH-functional polyesters and acrylates, acid-functionalresins, and hydroxyalkylamides.

In one embodiment involving ketone-hydrazine crosslinking, the amount ofketone crosslinkable functional groups in the polymer containingpolyamide and multiple urethane and/or multiple urea linkages will be atleast 0.05 milliequivalents per gram of said polymer dispersion, or upto about 1 milliequivalent, preferably from about 0.05 to about 0.5milliequivalent, and more preferably from about 0.1 to about 0.3milliequivalent per gram of said polymer dispersion. In that embodimentthe ketone groups can be on the polymer containing polyamide andmultiple urethane and/or multiple urea linkages and/or the polymer fromethylenically unsaturated monomers. In another embodiment, at least 10,20, 30, 40 or 50 wt. % of said polymer containing polyamide and multipleurethane and/or multiple urea linkages has at least one ketone groupchemically bonded to each polyurethane chain of said polyurethane. Inanother embodiment said polymer containing polyamide and multipleurethane and/or multiple urea linkages in the form of a dispersionfurther comprises hydrazine and/or hydrazide groups (sometimes in theform of low molecular weight species and sometimes in the form ofpolymers with hydrazide groups) in an amount from 10 mole % to about 100or 200 mole % of ketone groups in said polymer containing polyamide andmultiple urethane and/or multiple urea linkages in the form of adispersion. This provides for a ketone chemical reaction with hydrazineforming a chemical bond that can function as chemical crosslinking.Typically, when adding hydrazine for crosslinking one does not use anexcess of hydrazine because of potential undesirable reactions ofhydrazine on humans. In one embodiment, the amount of hydrazine orhydrazide groups is desirably from about 20 to 100 mole % of the amountof ketone functional groups.

In one embodiment, said hydrazine and/or hydrazide groups are part of areactive hydrazine or hydrazide compound of less than 400, 300 or 220g/mole molecular weight (such as adipic acid dihydrazide). In anotherembodiment, said hydrazide groups are present and said hydrazide groupsare part of a hydrazide reactive oligomeric or polymeric chemicalcompound of 300 or 400 g/mole to 500,000 g/mole molecular weight.

In another embodiment, said polymer from free radically polymerizablemonomers comprises on average one or more (more desirably up to about 1milliequivalent, preferably from about 0.05 to about 0.5milliequivalent, and more preferably from about 0.1 to about 0.3milliequivalent per gram of said polymer from free radicallypolymerizable monomers on a dry polymer weight basis) ketone groups perpolymer and said dispersion further comprises hydrazine and/or hydrazidegroups in an amount from 10 mole % to about 200 mole % based on themoles of said ketone groups.

The ketone-hydrazine crosslinking described above is well known in theurethane and acrylic polymer dispersion art as effective crosslinkersfor polymeric dispersions at around room temperature upon evaporation ofvolatile base and shift of the solution pH from slightly basic toneutral or pH acid. U.S. Pat. No. 8,901,244 teaches urethanes andrelated compounds in water crosslinked or increased in molecular weightby ketone-hydrazine crosslinking. This technology is also sometimesknown as azomethine linkages.

The polymer containing polyamide and multiple urethane and/or multipleurea linkages in the form of a dispersion may also comprise anionic,nonionic, or zwitterionic surfactants to help colloidally stabilize thedispersion.

Processes

The prepolymer of the polymer containing polyamide and multiple urethaneand/or multiple urea linkages of this disclosure are made in accordancewith this invention by forming the prepolymer from the reaction ofZerewitinoff reactive groups with polyisocyanates in the substantialabsence of water (as water reacts with isocyanate groups) and thendispersing this prepolymer in aqueous medium. This can be done in any ofthe methods known to the art. Typically, prepolymer formation will bedone by bulk or solution polymerizing the ingredients of the prepolymer.

Once the urethane prepolymer mixture is formed, optionally withdispersing moieties incorporated into said prepolymer/polymer, it isdispersed in an aqueous medium to form a dispersion or a solution.Dispersing the prepolymer in aqueous medium can be done by anyconventional technique in the same way that polyurethane prepolymersmade by bulk or solution polymerization are dispersed in water.Normally, this will be done by combining the prepolymer blend withaqueous medium with mixing. Where solvent polymerization is employed,the solvent and other volatile components can optionally be distilledoff from the final dispersion, if desired. Where the prepolymer includesenough water-dispersibility enhancing compound, e.g., anionic, cationic,and/or nonionic monomers, to form a stable dispersion without addedemulsifiers (surfactants), the dispersion can be made without suchcompounds, i.e., substantially free of surfactants of less than 200g/mole molecular weight, if desired. The advantage of this approach isthat the coatings or other products made from the polymer containingpolyamide and multiple urethane and/or multiple urea linkages withoutlow molecular weight surfactants exhibit less water sensitivity, oftenbetter film formation and less foaming.

Other known ways of making aqueous polyurethane dispersions can also beused to make the dispersions of this invention. Their review can befound in several publications including by D. Dieterich in Progress inOrganic Coatings, vol. 9, pp. 281-340 (1981). Examples of the processesinclude:

Shear Mixing—Dispersing the prepolymer by shear forces with emulsifiers(external emulsifiers, such as surfactants, or internal emulsifiershaving anionic, nonionic, cationic and/or zwitterionic groups as part ofor pendant to the polymer backbone, and/or as end groups on the polymerbackbone).

Acetone process—A prepolymer is formed with or without the presence ofacetone, MEK, and/or other polar solvents that are non-reactive withisocyanates and easily distilled. The prepolymer is further diluted insaid solvents as necessary, and chain extended with an activehydrogen-containing compound. Water is added to the chain-extendedpolymer, and the solvents are distilled off. A variation on this processwould be to chain extend the prepolymer after its dispersion intoaqueous medium.

Melt dispersion process—An isocyanate-terminated prepolymer is formed,and then reacted with an excess of ammonia or urea to form a lowmolecular weight oligomer having terminal urea or biuret groups. Thisoligomer is dispersed in aqueous medium and chain extended bymethylolation of the biuret groups with formaldehyde.

Ketazine and ketimine processes—Hydrazines or diamines are reacted withketones to form ketazines or ketimines. These are added to a prepolymer,and remain inert to the isocyanate. As the prepolymer is dispersed inwater, the hydrazine or diamine is liberated, and chain extension takesplace as the dispersion is taking place.

Continuous process polymerization—An isocyanate-terminated prepolymer isformed. This prepolymer is pumped through high shear mixing head(s) anddispersed into water and then chain extended at said mixing head(s), ordispersed and chain extended simultaneously at said mixing head(s). Thisis accomplished by multiple streams consisting of prepolymer (orneutralized prepolymer), optional neutralizing agent, water, andoptional chain extender and/or surfactant.

Reverse feed process—Water and optional neutralizing agent(s) and/orextender amine(s) are charged to the prepolymer under agitation. Theprepolymer can be neutralized before water and/or diamine chain extenderis added.

Additives and Applications

It may be desirable to include coalescing aids in the prepolymers andpolymer containing polyamide and multiple urethane and/or multiple urealinkages in the form of a dispersions of this disclosure to help promotecoalescence at the desired temperature of the polymer particles witheach other and with any solid additives in the compositions. Coalescingaids can also be known as solvents or plasticizers, depending on theirfunction. One coalescing aid is the free radically polymerizablemonomers (vinyl monomers) earlier discussed with composite polymerblends. Preferred vinyl monomers include methyl methacrylate, butylacrylate, ethylhexyl acrylate, ethyl acrylate and styrene. Coalescingsolvents include diethylene glycol dimethyl ether, dipropylene glycoldimethyl ether, dimethylcarbonate, isopropyl alcohol, dibutylene glycoldimethyl ether, and Texanol (isobutyric ester of2,2,4-trimethyl-1,3-pentanediol).

Neutralization agents can optionally be employed in the dispersions ofthe invention and the coating compositions prepared from suchdispersions. The pH of the compositions can range from about 7 to about10 if anionically stabilized. Suitable neutralization agents include butare not limited to alkali hydroxides such as lithium, sodium andpotassium, and organic bases such as ammonia and tertiary amines such astriethanolamine, aminomethyl propanol, dimethyl ethanol amine, trimethylamine, triethylamine morpholine, and mixtures thereof.

Crosslinkers

Compounds having at least one crosslinkable functional group can also beincorporated into the polyurea/urethane of the present invention, ifdesired. Examples of such compounds include those having carboxylic,carbonyl, amine, hydroxyl, epoxy, acetoacetoxy, olefinic and hydrazidegroups, blocked isocyanates, and the like, and mixtures of such groupsand the same groups in protected forms which can be reversed back intooriginal groups from which they were derived. Other suitable compoundsproviding crosslink ability include thioglycolic acid,2,6-dihydroxybenzoic acid, melamine and its derivatives, multivalentmetal compounds and the like, and mixtures thereof.

The amount of optional compounds having crosslinkable functional groupsin the prepolymer of the polymer containing polyamide and multipleurethane and/or multiple urea linkages will typically be up to about 1milli-equivalent, preferably from about 0.05 to about 0.5milli-equivalent, and more preferably from about 0.1 to about 0.3milli-equivalent per gram of final polymer(s) in the polyurethanedispersion on a dry weight basis.

Other additives well known to those skilled in the art can be used toaid in preparation of the dispersions of this invention. Such additivesinclude surfactants, stabilizers, defoamers, thickeners, levelingagents, antimicrobial agents, antioxidants, UV absorbers, fireretardants, pigments, dyes, and the like. These additives can be addedat any stage of the manufacturing process.

The dispersions of this invention typically have total solids of atleast about 20 weight percent in one aspect, at least about 30 weightpercent in another aspect, and at least about 40 weight percent in afurther aspect, and about 45 weight percent in still another aspect,based on the weight of the total coating composition.

As coating compositions or adhesives, they may be applied to anysubstrate including wood, metals, glass, cloth, leather, paper,plastics, foam and the like, by any conventional method includingbrushing, dipping, flow coating, spraying, and the like.

The gloss reading on the coatings and films of the current disclosurecan be accomplished according to ASTM D523-14. Measurements can be takenat geometry angles of 20, 60, or 85°. Desirably, the gloss values on a 3mil (0.076 mm) thick coating at 60° is less than 60, more desirably lessthan 40, and preferably less than 20. Desirably, the haze values isrelatively low at such gloss values, such that the haze value is lessthan 5, more desirably less than 4 or 3, and preferably less than 2.Conventional silica flattening agents with a 60° gloss of 20 wouldnormally generate a haze value above 5 or 10. Gloss is associated withthe capacity of a surface to reflect more light in directions close tothe specular than in others. Measurements correlate with visualobservations of surface shininess made at similar angles. Other visualaspects of surface appearances such as distinctness of reflected images,reflection haze and texture are involved in the assessment of gloss.Desirable substrates for measuring gloss and haze include cold rolledmetals (optionally primed), glass plates, polyester films such as Mylar,and Leneta charts (optionally black if haze is to be measured).

The compositions of the present invention and their formulations areuseful as self-supporting films, coatings, inks, and adhesives onvarious substrates with matting or gloss adjusted by the polyamide fromthe amine repeating units of Formulas I to IV. The compositions of thisdisclosure are particularly useful on wood and metal coatings whereprior art matting agents often add porosity or permeability of thecoating by staining materials or substrate damaging or corrodingmaterials such as water. The compositions of the current disclosure areparticularly useful in metal coatings use for transportation vehiclesand other original equipment manufacturers where low, medium, or highmatt finishes can contrast nicely with high gloss finishes in otherareas. The compositions of this disclosure are particularly useful onclear or highly transparent substrates where one wants to avoid glare orlight reflection onto other surfaces or obstruct/blur identification ofobjects on the other side of the substrate without reducing totaltransmitted light through the substrate. These polymer containingpolyamide and multiple urethane and/or multiple urea linkages have highlight transmission through the coating but with sufficient matting cansubstantially obstruct/blur objects on the other side of the substratebut still allow substantially all of the incident light to pass throughthe coating. Other prior art matting agents use mineral additives toadjust matting and these mineral additives have much higher refractiveindex than this polyamide and thus they reflect back more incident lightdue to difference in refractive index between the polymer binder andmatting agent.

Working Examples

In these examples, the following reagents were used:

H12MDI-1,1′-methylenebis-(4-isocyanato cyclohexane) from BayerCorporation as Desmodur® W

Hydrogenated dimer acid—DA

Sebacic acid—SA

Dodecanedioic acid—DDA

Caprolactone—CPL

4,4′-Methylenebis(cyclohexylamine)—MHMDA

4,4′-Methylenebis(2-methylcyclohexylamine)—HMDA

1,2-cyclohexanediamine—CHDA

Isophorone diamine—IDA

Polyketone diol is the reaction product of 2 moles of levulinic acidwith one mole of the diglycidylether of bisphenol A with 0.5-0.7 molesof a diisocyante to effect coupling.

Polycarbonate was Eternacoll PH100, which is an aliphatic polycarbonatesold by UBE believed to be about 1000 g/mole molecular weight diol withrepeat units of carbonate with 1,6-hexanediol and 1,5-pentanediol.

DMBA is dimethylolbutanoic acid.

Acrylate is a blend of 70 wt. % methyl methacrylate, 10 wt % ethyleneglycol dimethacrylate, and 20 wt. % octylacrylamide.

TEA is triethanolamine.

Hydrazine is H₂N═NH₂ and it is usually available as 35% active.

ADH is adipic acid dihydrazide and it usually comes as neat.

Polyketone diol synthesis example. A poly-ketone functional oligomer wasprepared by combining items 1-3 of the ingredients below in a 4 neckflask equipped with a thermometer, overhead stirrer and nitrogen gasinlet. With stirring and under a nitrogen blanket, the temperature ofthe reaction mixture was raised to 100° C. to 103° C. and held at thistemperature for 1 hour. The temperature was then raised to 110-114° C.and held there for an additional hour. Finally, the reaction mixture wasraised to 121-125° C. and held at this temperature for two hours oruntil the acid number was <1.0 (mg/g). At this point, item 4 was addedas a solvent, followed by the addition of item 5 at 90-94° C. to effectcoupling of the previously made oligomer. The temperature was raisedback up to 116-120° C. and maintained there until the titrated NCO forthe resulting product was <0.1% (or essentially nil). The final materialhad a slight amber color and a viscosity of ˜5,100 cps at 70° C.

Item # Material Parts MW Moles 1 Bisphenol A diglycidyl ether (Epon 828)331.4 376 0.88 2 Levulinic Acid 202.1 116 1.74 3 Triphenyl phosphine(TPP) 4.0 4 Benzyl Benzoate 152.6 5 1,6-Hexane Diisocyanate 73.2 168.20.43

Polyamide 1

The 4,4′-methylenebis(cyclohexylamine), hydrogenated dimer acid and thesebacic acid was added to a 2000 mL stirred reactor under nitrogen andheated to 180° C. The monomers were reacted until the acid number of thepolymer dropped below 1 (mgKOH/g). The water which formed during thereaction was allowed to evaporate from the reactor and the reactor wasplaced under vacuum for a short period of time to remove traces ofwater. Then caprolactone was charged and allowed to react for 6 hours.The final product is a yellowish polyamide oligomer.

Polyamide 2

The 4,4′-methylenebis(2-methylcyclohexylamine), hydrogenated dimer acidand the dodecanedioic acid was added to a 2000 mL stirred reactor undernitrogen and heated to 180° C. The monomers were reacted until the acidnumber of the polymer dropped below 1 (mgKOH/g). The water which formedduring the reaction was allowed to evaporate from the reactor and thereactor was placed under vacuum for a short period of time to removetraces of water. Then caprolactone was charged and allowed to react for6 hours. The final product is a yellowish polyamide oligomer.

Polyamide 3

The 4,4′-methylenebis(2-methylcyclohexylamine) and caprolactone wasadded to a 2000 mL stirred reactor under nitrogen and allowed to reactat 180° C. for 12 hours in the presence of titanium octoate(titanium(IV) 2-ethylhexyloxide at 200 ppm based on the weight of thereactants) catalyst. The final product is a yellowish polyamideoligomer.

Polyamide 4

The 4,4′-methylenebis(cyclohexylamine), piperazine and dodecanedioicacid was added to a 2000 mL stirred reactor under nitrogen and heated to180° C. The monomers were reacted until the acid number of the polymerdropped below 1 (mgKOH/g). The water which formed during the reactionwas allowed to evaporate from the reactor and the reactor was placedunder vacuum for a short period of time to remove traces of water. Thencaprolactone was charged and allowed to react for 12 hours in thepresence of titanium octoate catalyst. The final product is a yellowishpolyamide oligomer.

Polyamide 5

The 4,4′-methylenebis(cyclohexylamine), isophorone diamine anddodecanedioic acid was added to a 2000 mL stirred reactor under nitrogenand heated to 180° C. The monomers were reacted until the acid number ofthe polymer dropped below 1 (mgKOH/g). The water which formed during thereaction was allowed to evaporate from the reactor and the reactor wasplaced under vacuum for a short period of time to remove traces ofwater. Then caprolactone was charged and allowed to react for 12 hoursin the presence of titanium octoate catalyst. The final product is ayellowish polyamide oligomer.

Polyamide 6

The 1,2-diaminocyclohexane and dodecanedioic acid were added to a 2000mL stirred reactor under nitrogen and heated to 180° C. The monomerswere reacted until the acid number of the polymer dropped below 1(mgKOH/g). Then caprolactone was charged and allowed to react for 6hours. The final product is a yellowish polyamide oligomer.

Waterborne Polyurethane Dispersions General Procedure for Preparation ofPolymer Containing Polyamide and Multiple Urethane and/or Multiple UreaLinkages, Dispersion in Aqueous Medium, and Chain Extension

The polyamide and the polycarbonate was charged to the reactor andheated to 150° C. and mixed until a homogeneous mixture was obtained.The estimated molecular weight of each polyamdie is shown in Table I.The components in each polyamide is shown in Table II. Then the reactorwas cooled to 120° C. and Desmodur™ W was charged and reacted for 30minutes at 100° C. All acrylate monomers were added to the prepolymerand after the reactor became homogeneous the temperature was set to 85°C. and DMBA was charged. The recipe of the dispersions are shown inTable IV. The DMBA was allowed to react until the theoretical NCO wasreached then polyketone diol was added. Polyketone diol was allowed toreact until theoretical NCO was reached. Triethyl amine was added to theprepolymer and the batch was cooled to 65-75° C. and dispersed intowater to form a dispersion with 20-30 wt. % polymer and 70-80 wt. %water. The polyurethane was then chain extended with hydrazine and theacrylic polymerization was initiated by the addition oft-butylhydroperoxide, erithorbic acid and an EDTA-iron complex. 30minutes after the exotherm of the polymerization the temperature wasincreased to 50° C. and maintained until all monomers were reacted. Thefinal product is a milk white dispersion which forms a low gloss film.

TABLE I Molecular Weight of polyamide copolymers of examples 1-6determined by end-group analysis and mass determination. Mn(nominal)1100 Polyamide 1 1100 Polyamide 2 1000 Polyamide 3 900 Polyamide 4 900Polyamide 5 700 Polyamide 6

TABLE II 4,4′- 4,4′- 1,2 Hydro- Methylenebis(cyclo- Methylenebis(2-cyclo- Isophorone genated Sebacic Dodecanedioic Poly- hexylamine)-methylcyclohexylamine)- hexanediamine- diamine- Piperazine- dimer acid-acid- Caprolactone- amide MHMDA HMDA CHDA IDA PIP acid-DA SA DDA CPL 1419.9 g 300.3 g 113.9 g 207.4 g 2 442.2 g  282.3 103.8 g 207.4 3 239762.7 4 289.1 12.2 g 56.1 653.4 5 199.3 66.7 g  26.9 g 713.3 6 353.5 g387.7 322.2

TABLE III Polyamide Polyamide Dispersion internal code code internalcode Dispersion Polyamide 1 Dispersion 1 Polyamide 2 Dispersion 2Polyamide 3 Dispersion 3 Polyamide 4 Dispersion 4 Polyamide 5 Dispersion5 Polyamide 6 Dispersion 6

TABLE IV Dis- Poly- Poly- Polyketone Desmodur ® persion amide carbonatediol W DMBA Acrylates TEA Water Hydrazine ADH 1 73.1 g 73.1 g 48.1 g165.4 g 20.6 g 210 g 15.5 g 1032 g 27.3 g 9.5 g 2 324 324 162 649 61.9840 55.7 3780 40.5 30.4 3 76.6 26.5 26.5 110.6 10.3 140 8.9 636 17.9 5 453 26.5 53 111 10 140 8.9 636 17.9 5 5 53 26.5 53 111 10 140 8.9 63617.9 5 6 52 26 52 113 10.3 140 8.9 626 17.1 4.6

Acrylate is a blend of 70 wt. % methyl methacrylate, 10 wt % ethyleneglycol dimethacrylate, and 20 wt. % octylacrylamide.

TABLE V Coatings were made from Dispersions 2-6 and applied on a Lenetachart (black) substrate at about 3 mils (0.003 inches, 0.076 micrometers(conversion 25.4)) thickness and the gloss and haze values were measuredaccording to ASTM D523-14 using a Elcometer 408. Dispersion Sample Gloss(60) Haze Dispersion 2 6.3 — Dispersion 3 18 4.6 Dispersion 4 15 2.1Dispersion 5 7 0.8 Dispersion 6 12 1.5

Except in the Examples, or where otherwise indicated, all numericalquantities in this description specifying amounts, reaction conditions,molecular weights, number of carbon atoms, etc., are to be understood asmodified by the word “about.” Unless otherwise indicated, all percentand formulation values are on a molar basis. Unless otherwise indicated,all molecular weights are number average molecular weights. Unlessotherwise indicated, each chemical or composition referred to hereinshould be interpreted as being a commercial grade material which maycontain the isomers, by-products, derivatives, and other such materialswhich are normally understood to be present in the commercial grade.However, the amount of each chemical component is presented exclusive ofany solvent or diluent, which may be customarily present in thecommercial material, unless otherwise indicated. As used herein, theexpression “consisting essentially of” permits the inclusion ofsubstances that do not materially affect the basic and novelcharacteristics of the composition under consideration. All of theembodiments of the invention described herein are contemplated from andmay be read from both an open-ended and inclusive view (i.e., using“comprising of” language) and a closed and exclusive view (i.e., using“consisting of” language). As used herein parentheses are useddesignate 1) that the something is optionally present such thatmonomer(s) means monomer or monomers or (meth)acrylate meansmethacrylate or acrylate, 2) to qualify or further define a previouslymentioned term, or 3) to list narrower embodiments.

While certain representative embodiments and details have been shown forthe purpose of illustrating the subject invention, it will be apparentto those skilled in this art that various changes and modifications canbe made therein without departing from the scope of the subjectinvention.

What is claimed is:
 1. A colloidally stabilized polymer dispersion in anaqueous medium, said polymer containing a polyamide oligomer andmultiple urethane linkages and/or multiple urea linkages, saiddispersion in aqueous medium comprising a) a polyamide oligomer havingamine repeating units selected from

wherein R₁ to R₅ are independently selected from H or a C₁ to C₄ linearor branched alkyl group, wherein the nitrogen terminal groups of saidamine repeating units are reacted with reactive carbonyl repeating unitshaving at least one carbonyl group capable of forming an amide linkage;b) at least one repeating unit from a polyisocyanate reacted with ahydroxyl or amine group; and c) a water dispersible group reacted intosaid polymer containing polyamide and multiple urethane and/or multipleurea linkages; further wherein said amine repeating units are a portionof said polymer containing polyamide and multiple urethane and/or urealinkages and said amine repeating units are from about 4 to about 15 wt.% of said polymer containing polyamide and multiple urethane and/ormultiple urea linkages; further wherein at least one of said aminerepeating groups of said polyamide oligomer is connected to repeatingunits of the formula —(C(═O)—R_(e)—C(═O)— derived from a dicarboxylic inan alternating sequence, wherein R_(e) is a C₃ to C_(48 or 58) linear orbranched alkylene group; further wherein the polyamide oligomer isfurther reacted with a cyclic lactone or hydroxycarboxylic acid of 2 to15 carbon atoms to chain extend the polyamide oligomer with polyesterrepeating units, wherein said polyester repeating units are from 1 to 75wt. % of said polymer containing polyamide and multiple urethanelinkages and/or urea linkages.
 2. The polymer dispersion in aqueousmedium according to claim 1, wherein said polyamide oligomer on averagehas from about 1 to about 10 total of said amine repeating units ofFormula I or Formula II per polymer chain.
 3. The polymer dispersion inaqueous medium according to claim 1, wherein at least one of said aminerepeating groups of said polyamide oligomer is connected to repeatingunits of the formula —C(═O)—R_(f)—O— wherein R_(f) is a C₁ to C₁₄ linearor branched alkylene group.
 4. The polymer dispersion according to claim1, wherein said polymer further comprises a) one or more polyestersegment, b) one or more polycarbonate segment, c) one or more polyethersegment, or d) blends thereof chemically bound into said polymer orphysically blended with said polymer of said dispersion, wherein saidpolyester, polycarbonate, or polyether segment, or blends thereofcomprise from about 2 to about 50 wt. % of the total polymer weight ofsaid polymer dispersion.
 5. The polymer dispersion according to claim 1,wherein said polymer dispersion further comprises unsaturated freeradically polymerizable monomeric reactants or polymeric species derivedfrom said unsaturated free radically polymerizable monomeric reactantsin an amount from about 10 to about 50 wt. % based on the total weightof polymer in said dispersion.
 6. The polymer dispersion according toclaim 1 further comprising a crosslinking agent or crosslinkable groupthat facilitates crosslinking built into the polymer.
 7. The polymerdispersion according to claim 1 further comprising at least 5 wt. % ofpolyamide having tertiary amide repeating units of the structure

wherein R_(a) is the alkylene portion of the dicarboxylic acid and is acyclic, linear, or branched alkylene of 2 to 58 carbon atoms, andwherein R_(b) is a linear or branched alkylene group of 2 to 60 carbonatoms and R_(c) and R_(d) are individually a linear or branched alkylgroup of 1 to 8 carbon atoms, or R_(c) and R_(d) connect together toform a single linear or branched alkylene group of 1 to 8 carbon atoms.8. The polymer dispersion in aqueous medium according to claim 7,wherein at least 60 mole % of the repeating units of the tertiary amidestructure, said repeating units having the structure

are cyclic tertiary amide repeating units where R_(b) has from 2 to 6carbon atoms and R_(c) and R_(d) connect together to be a linear orbranched alkylene group of 1 to 4 carbon atoms.
 9. The polymerdispersion in aqueous medium according to claim 1, wherein said waterdispersible group is selected from the group of anionic, cationic,nonionic, or blends thereof.
 10. The polymer dispersion according toclaim 1, wherein said water dispersible group comprises an anionic waterdispersing covalently bound into or synthesized into said at least onepolymer of said polymer dispersion.
 11. The polymer dispersion accordingto claim 9, wherein said anionic water dispersing group comprises acarboxylic acid present at an acid number from about 5 to about 40 mgKOH/g of polymer.
 12. The polymer dispersion according to claim 9,wherein said water dispersible group comprises a nonionic oligomercovalently bound into or synthesized into said at least one polyurethaneof said polymer dispersion.
 13. The polymer dispersion according toclaim 9, wherein said water dispersible group comprises a cationic waterdispersing groups.
 14. The polymer dispersion of claim 4, wherein saidpolymer comprises polycarbonate segments of 500 to 5,000 g/molemolecular weight present in an amount from about 2 to about 50 wt. % ofthe total polymer weight of said polymer containing polyamide andmultiple urethane and/or multiple urea linkages of said dispersion. 15.The polymer dispersion according claim 1 further comprising at least 10wt. % of a second polymer based on the total weight of polymers in saidpolymer containing polyamide and multiple urethane linkages and/ormultiple urea linkages in the form of a dispersion, said second polymerhaving less than 4 wt. % of amine repeating units of Formula I andFormula II.
 16. The polymer dispersion according to claim 15, wherein atleast 50 wt. % of said second polymer exists in separate dispersedpolymer particles in the aqueous phase and at least 50 wt. % of saidseparate dispersed polymer particles contain less than 4 wt. % ofcombined amine repeating units of Formula I and Formula II.
 17. Thepolymer dispersion according to claim 15, wherein at least 50 wt. % ofsaid second polymer co-exists in polymer particles with said polymercontaining polyamide and multiple urethane and/or multiple urealinkages, said polymer containing polyamide and multiple urethanelinkages and/or multiple urea linkages being characterized by havingfrom about 4 to about 15 wt. % of amine repeating units of Formula Iand/or Formula II.
 18. The polymer dispersion according to claim 15,wherein said second polymer is a polyurethane polymer.
 19. The polymerdispersion according to claim 15, wherein said second polymer is apolymer formed from free radically polymerizing unsaturated monomer(s).20. The polymer dispersion according claim 1 formed into aself-supporting film, coating, or adhesive.
 21. The polymer dispersionaccording to claim 20 converted into a self-supporting film or coatingon a substrate by forming into the appropriate shape and evaporating theaqueous medium; said film or coating having a gloss reading at 60° ofless than 20 using for a film or coating thickness of 3 mils accordingto ASTM D523-14 using an elcometer
 408. 22. The polymer dispersionaccording to claim 21 in the form of a coating on a substrate whereinsaid substrate is a metal, wood, clear plastic, or clear glass.
 23. Thepolymer dispersion according to claim 1, wherein at least 80 molepercent of the R₅ groups of said amine repeating units are H.